Chapter 4

Joule Thomson Effect

Chemical Potential
Fugacity

Chapter11111
Chapter 1 1: Slide
: Slide1
Chemical Thermodynamics : Georg Duesberg 1
 Joule Thomson Effect
Refrigeration developed by Carl von Linde in 19th
Century, in response to a request from Guinness
in Dublin for a new cooling technique.
Based upon the fact that gases cool as they
expand: Joule-Thomson effect (William
Thomson, later Lord Kelvin, born in Belfast),

The Linde refrigerator combines the JT process

with a counter-flow heat exchanger.
The gas is re-circulated and it cools on expansion
through the throttle. The cooled gas cools the high-
pressure gas, which cools still further as it
expands. Eventually liquefied gas drips from the
throttle.
Chemical Thermodynamics : Georg Duesberg
2
 Heat capacities
From first law of thermodynamics:

dU dQ dW with dW PdV H U pV
dU dQ pV
U U H H
dU dT dV dH dT dp
T V V T T p p T
U Heat capacity at H Heat capacity at
CV CP
T V constant volume T P constant pressure
(isochore) (isobar)

U H
dU CV dT dV dH C p dT dp
V T p T
 Change of Internal Energy at constant temperature
for ideal gases
No interactions between molecules.
the internal energy of gas depends on temperature only.
Z = 1; PV = RT
U = U (T)
U U
dU dT dV
T V V T
Heat capacity at U U Internal Pressure
constant volume CV T of a gas
T V V T
(0 for ideal gas)
dU CV dT T dV
[Note from VdW: a(n2/V2)= T ]

Chemical Thermodynamics : Georg Duesberg

 Internal Pressure, T
For ideal gas, T = 0 because U
independent of molecular separation
for volume changes at constant T
Implies ideal gas law
For real gas,
If dU >0 as dV increases with T
constant, attractions between
molecules dominate and T > 0
If dU <0 as dV increases with T
constant, repulsions between
molecules dominate and T <0

[Note from VdW: a(n2/V2)= T ]

Chemical Thermodynamics : Georg Duesberg
 Joule Experiment: Measure T


V2

pex = 0, therefore w = 0 w p ex dV
V1
dT=0, therefore q = 0
DU = q +w = T dV= 0
T must =0 since dV>0

No change in temperature occurs when

air is allowed to expand in such a manner
as not to develop mechanical power J. P.
Joule, Phil. Mag., 26, 369 (1845)

Joule experiment incapable of detecting

small effects since the water calorimeter he
used had a large heat capacity pex = 0

Chemical Thermodynamics : Georg Duesberg

 THE JOULE-THOMPSON EXPERIMENT
A further test of intermolecular forces in real gases.
H H
DH DT DP 0
T P P T
Imagine a sample of gas pushed through a porous
plug, in an isolated tube (adiabatic system). The
temperature is measured on each side of the plug.
Analysis
w = piVi - pfVf
Since DU = Uf - Ui = w (because q = 0),
Uf + pfVf = Ui + piVi
Hf = Hi i.e. DH = 0
This is a constant enthalpy (isenthalpic) process.

What is
H H
CP ???
T P P T
Chemical Thermodynamics : Georg Duesberg
 Thermodynamic Consequences of State Functions
Enthalpy, H(p,T) H H H
DH DT DP 0 ???
T P P T P T
To evaluate (dH/dp)T we apply Euler chain rule:

T

H P H H T H
CP
p T T T p P H T P

H p T
JT
P H
Cp= (dH/dT)p and one defines (dT/dP)H as as Joule Thomson Coefficient
then (dH/dp)T =- Cp, is the Isothermal Joule Thomson Coefficient

H
JT CP
P T
Chemical Thermodynamics : Georg Duesberg
 Joule Thompson Experiment

Modern methods measure CP (Isothermal)

not
Isothermal J-T coefficient, T = (dH/dp)T
= -Cp
Practical applications: Gas liquification,
Isotope separation, artificial snow

Chapter99999 1 : Slide
Chemical Thermodynamics : Georg Duesberg 9
 - Physical consensus
is a function of p and T (see Fig. for CO2)
can be either (+) or (-)
Positive means dT is negative when dp is
negative
Gas cools on expansion
Negative means that means dT is
positive when dp is negative
Gas warms on expansion
Transition between positive and negative
is called the Joule-Thompson inversion
temperature (Ti =2TB )
Gases have both high and low inversion
temperatures
Chemical Thermodynamics : Georg Duesberg
 Joule-Thomson Process for the vdW Gas
The JT process corresponds to an isenthalpic expansion:
H H
H
DH
H
DT DP 0
CP CP DT DP
T P P T
T P P T

H H V DH TDS VDP
T V
T P P T T P
T
H

S
T V
P H H Cp Cp P T P T

T p
S V
(Maxwell relation)
P T T P

This is a pretty general (model-independent) result. By applying this result to the vdW equation,
one can qualitatively describe the shape of the inversion curve (requires solving cubic
equations...).

V May be obtained form the equation of state

T P
 Joule-Thomson Process for the vdW Gas

Well consider the vdW gas at low densities: N 2a

P 2 V Nb
V
N 2a N 2a
P 2 (V Nb ) Nk BT PV PNb Nk BT (...)P
V V T

V N 2 a V V Nk B
P 2 Nk B
T P V T P P P
2
T N a
V2

V Na
T V Nb 2 a b
T T P 2
k BT
P H Cp RT
CP CP
 Joule-Thomson Process for the vdW Gas
2a 2a
Cooling: JT b 0 Heating: JT b 0
k BT k BT

If b = 0, T always decreases in the JT process: an increase of Upot at the expense of K.

If a = 0, T always increases in the JT process (despite the work of molecular forces is 0):

The upper inversion temperature:

(at low densities)

2a 27
TINV TC 2TB
k Bb 4
Tc =8a/27Rb
the critical temperature of the vdW gas
TB = a/Rb

Thus, the vdW gas can be liquefied by

compression only if its T < 27/4TC.

Chemical Thermodynamics : Georg Duesberg

 The JT Process in Real Gases

In real gases, molecules interact with each vdW gas

Upot
other. x
At low densities, the intermolecular forces expansion
are attractive. When the gas expands
adiabatically, the average potential energy
increases, at the expense of the kinetic energy. H U kin U pot PV
Thus, the temperature decreases because of
the internal work done by the molecules JT 0
during expansion.
 The JT Process in Real Gases
JT 0
At high densities, the effect is reversed: the free Upot
expansion results in heating, not cooling. The overall x
situation is complicated: the sign of DT depends on initial T
and P. expansion

All gases have two inversion temperatures: in the

range between the upper and lower inversion
heating temperatures, the JT process cools the gas, outside
this range it heats the gas.

cooling
isenthalpic curves Gas boiling T inversion T
(H =const) for (P=1 bar) @ P=1 bar
ideal and CO2 195 (2050)
real gases
CH4 112 (1290)
O2 90.2 893

For T < TINV, the N2 77.4 621

drop in pressure H2 20.3 205
(expansion) results 4He 4.21 51
in a temperature 3He 3.19 (23)
drop.
Chemical Thermodynamics : Georg Duesberg
 Liquification of Gases
Most gas liquifiers combine the expansion engines with JT process: the expansion
engine helps to pre-cool the gas below the inversion T. The expansion engines are a
must for He and H2 liquefiers (the inversion T is well below RT).

For air, the inversion T is above

RT. In 1885, Carl von Linde
liquefied air in a liquefier based
solely on the JT process: the gas
is recirculated and, since T is
below its inversion T, it cools on
expansion through the throttle. Linde
The cooled gas cools the high- refrigerator
pressure gas, which cools still
further as it expands. Eventually
liquefied gas drips from the
throttle.

Chemical Thermodynamics : Georg Duesberg

 Virial Equation of State and Joule Thompson
Virial coefficients:

Z = p Vm / RT = (1 + Bp + Cp2 + ...)

Z = p Vm / RT = (1 + B/Vm + C/Vm2 + ...)

For Low pressures (0-15 bar) B is
sufficient
for moderate pressures (<100 bar) B
and C describe Z well
High Pressure better use other EOS
Also allow derivation of exact correspondence
between virial coefficients and intermolecular
interactions.
dB(T )
JT p 0 B(T ) T
dT
Chemical Thermodynamics : Georg Duesberg
 The Perfect gas and T, a, kT,

Property Acr Value for Perfect Gas Info:

Internal U
Pressure T

T=0 Strength/nature of
V T interactions between
molecules

Expansion 1 V a =1 / T
The higher T, the less
Coefficient a responsive is its volume
V T p to a change in
temperature

1 V
Isothermal
Compressibility
kT
V p T
kT=1 / p The higher the p, the
lower its compressibility

T
Joule-Thomson


=0 Another indication of
Coefficient H
p molecular interactions.

Chemical Thermodynamics : Georg Duesberg

 Chemical Potential

Chapter1919191919
Chapter 1 : Slide 119:
Chemical Thermodynamics : Georg Duesberg Slide 19
 Chemical potential (m)
Energy status of molecules in a system (e.g. Benzene in
water)
Internal energies
Chemical Bonds, vibrations, flexations, rotations.
External Energies
Whole molecule transitions, orientations
Interactions of molecule with surroundings
Energy status is a function of:
Temperature
Pressure
Chemical composition
Average energy per molecule
Chemical Thermodynamics : Georg Duesberg
 Chemical Potential definition

No way to directly measure chemical potential.

Can only determine differences in , based on the
tendencies of a chemical to move from one situation to
another.
Need a reference point, like sea level or absolute zero.
often: select pure liquid chem. as reference

For a pure substance Gm

Chapter 1 : Slide 21
Chemical Thermodynamics : Georg Duesberg
 Chemical Potential
dG = (i i) dni

In a spontaneous processes, dG < 0 at constant T and P. dni moves

from phase to phase to have negative change in free energy.

The spontaneous transfer of a substance takes place from a region with

a higher i to a lower i. The process continues to equilibrium where
dG = 0, and i and i become equal.

Phase Phase
 If two populations of a chemicals (for example, the chemical
coexists in two separate phases): each will have its own value of
1 and 2
1: liquid 2: gas

1 2
Start: liquid benzene (1) and very little vapor benzene (2)
Initial disequilibrium: 1 2 (1 > 2)
Open stopcock. Benzene volatilizes. Net movement of benzene to the right.
1 decreases, 2 increases until they are equal till there is no net movement
of benzene

Chemical Thermodynamics : Georg Duesberg

 Chemical Potential
Partial molar Gibbs energy Chemical potential for component 1
G
1
n1 T , p ,n j

If T and p are kept constant (i.e. dT and dp = 0) then

G G
dG dn1 dn2 ...
n1 T , p ,n j n2 T , p ,n j

Or: dG 1dn1 2 dn2 ...

G 1n1 2 n2 ...
The total free energy is the sum of the contributions from all the
different components present:

G( P, T , ni ) ni i Chapter 6 : Slide 24
Chemical Thermodynamics : Georg Duesberg
 Chemical potential = free energy added to system with each added
increment of i
For a single component system containing 1 mole of substance:
Gm

G
i T , P, ni
ni
Where = chemical potential (kJ/mol)
DG = free energy (kJ)
ni = moles of component (i)

i Gi H i T Si
Chemical Thermodynamics : Georg Duesberg
 Properties of the Gibbs energy
G = H - TS H = U + pV

dH = dU +pdV + Vdp
dG = dH TdS - SdT
dqrev =TdS and dwrev = - pdV
Both are not state functions but the sum
dG = dU + pdV + Vdp TdS - SdT dq + dw can be treated to be reversible
because they only depend on the state
functions

dG = TdS pdV + pdV + Vdp TdS - SdT dU = TdS pdV

dG = Vdp - SdT G = f ( p, T )
26
Chemical Thermodynamics : Georg Duesberg
 Properties of the Gibbs energy
dG = Vdp - SdT

G G
S V
T p p T

G G
Slope = -S
Slope = V

T (constant p) P (constant T)
S is positive (-S is negative) V is positive so G is
so G is decreasing with increasing with
27
increasing T increasing p
Chemical Thermodynamics : Georg Duesberg
 Dependence of G on p
It would be useful to determine the Gibbs energy at one
pressure knowing its value at a different pressure.

dG = Vdp - SdT

We set dT = 0 (we make sure that the temperature is steady

and integrate:
Gf pf

Gi
dG Vdp
pi

pf
DG Vdp
pi

pf
G( pf ) G( pi ) Vdp
pi
28
Chemical Thermodynamics : Georg Duesberg
 Dependence of G on p
pf
G( pf ) G( pi ) Vdp
pi

Liquids and Solids.

Only slight changes of volume with pressure mean that we can effectively
treat V as a constant.

G( pf ) G( pi ) VDp

G( pf ) G( pi ) V ( pf pi )

Often V Dp is very small and may be neglected i.e. G for solids and liquids
under normal conditions is independent of p. Exception: Geography
29
Chemical Thermodynamics : Georg Duesberg
 Dependence of G on p
pf
G( pf ) G( pi ) Vdp
pi

Ideal Gases.

For gases V cannot be considered a

constant with respect to pressure.
For a perfect gas we may use:
dp pf
G ( pf ) G ( pi ) nRT
pi p

pf
G ( pi ) nRT ln
pi
30
Chemical Thermodynamics : Georg Duesberg
 Dependence of G on p
Ideal Gases.
pf
G( pf ) G( pi ) nRT ln
pi

We can set pi to equal the standard pressure, p ( = 1 bar).

Then the Gibbs energy at a pressure p is related to its
standard Gibbs energy, G, by:

pf
G ( pf ) G nRT ln
p

Chemical Thermodynamics : Georg Duesberg

 Fugacity (lat.) = urge to flee same
units as pressure

The fugacity is a parameter which enables us to apply the perfect gas

expression to real gases.
In the thermo dynamical treatment of the Chemical Potential

Chemical Thermodynamics : Georg Duesberg

 Dependence of G on p
Real Gases.

For real gases we modify the

expression for a perfect gas and
replace the true pressure by a new
parameter, f, which we call the
fugacity.
f
Gm ( pf ) Gm RT ln
p
The fugacity is a parameter we
have simply invented to enable us
to apply the perfect gas expression
to real gases.
33
Chemical Thermodynamics : Georg Duesberg
 Dependence of G on p
Real Gases.
f2
We may then write DG RT ln
f1
We may show that the ratio of fugacity to pressure is called the fugacity
coefficient:

f

p Where is the fugacity coefficient

is related to the compression factor Z and the Viral coefficients:

p Z 1
ln dp f pe B ' p C ' P 2 ..)
0 p Viral coefficients
Chemical Thermodynamics : Georg Duesberg
 A real gas is in its standard state when its fugacity is equal to 1 bar and it is
behaving as if it were an ideal gas at some specified temperature (the
diagram shown below is exaggerated to make this point):

hypothetical ideal gas fi In the limit of zero pressure real

fugacity = Pi
standard state gases behave more and more like
ideal gases and the fugacities of
real gas real gases approach their partial
f = 1 bar
pressures: lim fi --> Pi
not the standard state Pi --> 0

P = 1 bar pressure

The standard state of a pure liquid or solid at a fugacity of 1 bar and some
specified temperature. Since the molar volumes of solids and liquids are
generally small and relatively insensitive to pressure, the activities of solids and
liquids at pressures that are not too far removed from 1 bar remain close to
unity.
Chemical Thermodynamics : Georg Duesberg
 Pressure region Z f a

I (very Low) 1 P 0 0

II (moderate) <1 <P >0 >0

III (high) >1 >P <0 <0

Chemical Thermodynamics : Georg Duesberg

 Dependence of G on T
Using the same procedure as for the
dependence of G on p we get:

G To go any further we
S dG SdT need S as a function of T
T p ?

Instead we start with: G = H - TS

-S = (G H)/T

37
Chemical Thermodynamics : Georg Duesberg
 Dependence of G on T

GH
S
T (G / T ) H
2
T p T
G H
S
T T This is the Gibbs-Helmholtz
Equation
H
Let G/T = x x S
T (DG / T ) DH
2
T p T
x H
2
T p T

38
Chemical Thermodynamics : Georg Duesberg
 Dependence of G on T
Two expressions: DG (DG / T ) DH
DS 2
T p T p T
Gibbs-Helmholtz Equation
Changes in entropy or, more commonly, changes in enthalpy can be used
to show how changes in the Gibbs energy vary with temperature.

For a spontaneous (DG < 0) exothermic reaction (DH < 0) the change in
Gibbs energy increases with increasing temperature.

Less negative Slope = -DH/T2 = positive for exothermic reaction

DG/T
Very negative
T (constant p)
39
Chemical Thermodynamics : Georg Duesberg
Chemical Thermodynamics : Georg Duesberg
 Comparing the chemical potential of the real gas to the chemical
potential of an ideal gas at the same pressure

real id RT ln f (P)

( RT ln (P

P
))

The chemical potential of a real gas is

written in terms of its fugacity

J o RT ln f J
The activity coefficient (J) relates the
activity to the concentration terms of interest.
In gaseous systems, we relate the fugacity (or activity) to the ideal
pressure of the gas via
J PJ f J
Chemical Thermodynamics : Georg Duesberg
 Change in Internal Energy @ Constant P
Suppose we want to know how the internal energy, U, changes with temperature at
constant pressure
dU dV C dT
T V

U ( dV C dT)
T V

T
p T p

U V
T CV
T p T p

But the change in volume with temperature 1 V V

a or aV
at constant pressure is the related to the V T T
p p

thermal compressibility of the gas, a U

so a V C
T p
T V

Large a means sample responds strongly to changes in T

For an ideal gas, T = 0 so
U U
C V definition
T p T p
 Thermodynamic Consequences of State Functions
Enthalpy, H(p,T)
Like U, H is a state function By analogy to a earlier, the isothermal
compressibility, kT,
For closed system with constant composition 1 V V
H H kT or k T V
dH dp dT V p T p T
p T T p
so
H p
but Cp 1
T p
T V T
kT V
H V p
so dH dp C p dT
At constant volume p T

y 1
by reciprocal identity , x ,
H H p
Cp x z
T V p T T V y z
By the chain rule, we can find (dp/dT)V
T 1 V

V p V and we know T aV
y x z
T p
p
Chain Rule : if z z(x, y) then 1
x z z y y x
T 1
so
Re call p(V, T) V p a V
p 1 p a
This makes
T V T V T V k T
H a
V p p T H
and Cp
T V p T k T
 Thermodynamic Consequences of State Functions
Enthalpy, H(p,T)
To evaluate (dH/dp)T apply chain rule and reciprocal identity again
H 1
Euler chain rule
p T T p

H p T H
H H T
reciprocal relation 2x
p T T p p H

But, Cp= (dH/dT)p and if one defines (dT/dP)H as , then (dH/dp)T =- Cp

Thus,
H H a
Cp
T V p T k T
H a
C p Cp
T V kT
or
H a
C p 1
T V kT
 U U
dU dT dV
T V V T
1 V

V T P
U U U
Cv
T p V T T p

U U
C V
T p V T
v

1 V
k
V P T
H
(1 JT / k )C p
T V

45
 A Word about kT
We know that if we increase the pressure the volume decreases so if
dp is positive, dV is negative
Since kT(1/V)(dV/dp)T, kT is always positive
For and ideal gas V=nRT/p so
(dV/dp)T= -nRT/p2 and kT(1/V)(-nRT/p2 )
Simplifying kT,
kT (nRT /V)(1/p2 )
kT (p)(1/p2 )
kT (1/p )
This means that as the pressure increases, the compressibility
of a gas decreases